N,N{40 -Substituted 2,4,5-triketoimidazolidines

ABSTRACT

The invention relates to a process for the preparation of a N, N&#39;&#39;-substituted 2,4,5-triketoimidazolidine which comprises reacting an oxamidate ester with an isocyanate or an isocyanateforming in the presence or absence of a catalyst, at temperatures of -20* to +280*C, a product obtained therefrom and a shaped article containing it as the essential ingredient.

11391 States Pate [191 Reese et a1.

[ N,N '-SUBSTITUTED 2,4,5-TRIKETOIMIDAZOLIDINES [75] Inventors: Johannes Reese,

Wiesbaden-Biebrich; Kurt Kraft, Auringen, both of Germany Apr. 2, 1969 Germany 1916932 Apr. 24, 1969 Germany 1920845 [52] US. Cl.....'... 2611/3095; 260/77.5 R; 260/78 F; 260/248 NS; 260/287 R; 260/295 D; 260/304; 260/305 [51] Int. C1. C07D 233/96 [58] Field of Search 260/309.5

[56] References Cited UNITED STATES PATENTS 2,885,817 7/1959 Luckenbaugh 260/309.5 3,418,334 12/1968 Stoffel 260/309.5

OTHER PUBLICATIONS Biltz et al., Berichte 1913, Vol. 46, pages 1387-91 &

[ Dec. 23, 1975 1398-1400 relied on. QD1.D4.

Biltz et al., Chem. Abst. 1913, Vol. 7, pages 2574-5. QD1.A51.

Nagele, Chem. Abst. 1912, Vol. 6, pages 3422-3. QD1.A51.

Patton, J. Org. Chem. 1967, Vol. 32, pages 383-8. QD241.J6.

Stieger, Chem. Abst. 1917, Vol. 11, pages 1137-8. QD1.A51.

Stoffel, J. Org. Chem. 1964, Vol. 29, pages 2794-6. QD241'J6.

Fosse et al., Chem. Abst. 1935, Vol. 29, colmn. 4741.

Primary Examiner-Natalie Trousof Attorney, Agent, or FirmLittlepage, Quaintance, Murphy & Dobyns [57] ABSTRACT The invention relates to a process for the preparation of a N,N-substituted 2,4,5-triketoimidazolidine which comprises reacting an oxamidate ester with an isocyanate or an isocyanate-forming in the presence or absence of a catalyst, at temperatures of 20 to +280C, a product obtained therefrom and a shaped article containing it as the essential ingredient.

6 Claims, No Drawings 1 N,N '-SUBSTITUTED 2,4,5-TRIKETOIMIDAZOLIDINES This application is a continuation-inpart of application Ser. No. 24,794, filed on Apr. 1, 1970 which is now abandoned.

The invention relates to N, triketoimidazolidines.

It has been proposed to obtain 2,4,5-triketoimidazolidines of formula N-substituted 2,4,5-

in which R and -R' are the same or different and are selected from aromatic, cycloaliphatic and aliphaticgroups, either of which may also be substituted, according to the following processes:

I. By reaction of N,N'-disubstitute chloride:

d ureas with o ralyl -2 HCl l 2. By reaction of N,N-substituted ureas with ethoxalyl chloride:

3. By reaction of N,N'-substituted ureas with dialkyl oxalates:

2 alkanol In additiomthere are a number of complicated syntheses which start from substituted thioureas. They have not acquired any importance.

The reaction according to (1) requires oxalyl chloride which is expensive and due to its sensitivity to hydrolysis, difficult to handle. I

In addition, the ureas to be used as reaction components have to be synthesised. This neccesitates purification operations'particularl y with asymmetrically substituted types, in order to remove by-products.

The reaction according to (2) requires ethoxalyl chloride which is likewise expensive and can only be prepared from oxalyl chloride. Otherwise the statements made about reaction (1) also apply here.

The reaction according to (3) would as such be a convenient method but due to the low reactivity of the esters it only succeeds in a few cases. The yields are low and the reaction times extremely long.

A further disadvantage is commonto allthree methods; in many cases the ureas-used as starting materials are sparingly soluble compounds which, after an incomplete reaction to form the- 2,4,5-tr'iketoimidazolidines, can only be separated therefrom with difficulty.

Now according to the invention there is provided a compound ofgeneral formula R"-NYN wherein one of 0,0 is the. group NH co ,oR'Y

and the other NHCOCOOR", wherein R and R" are aliphatic hydrocarbon groups with up to 18 more than onetriketoimidazolidine ring. b. a monoor polynuclear monoto hexavalent aromatic radical having up to 20 carbon atoms being substituted by at least one substituent selected from halogen, nitro, cyano, dialkyla'mino, diarylamino, alkylarylamino, alkyl, 'haloalkyl,

alkylsulphonyl, alkoxy, alkylester, arylester, acyl, and cycloalkyl groups having up to 18 carbon atoms, a (w m) ketoalkyl radical having up to 5 carbon atoms, wherein the substitution by at least one halogen atom or at least one alkyl radical in a mononuclear aromatic radical is present only in a compound bl. having more than one triketoimidazolidine ring or b2. in a compound having at least one substituent of the group alkoxy, alkylester, alkylsulphonyl, nitro, and CF c. A monoto hexavalent unsubstituted heteroaromatic radical selected from the group benzo-' thiazolyl, phenyl, thiophenyl, benzofuryl, N- methylcarbazolyl, quinolyl, pyridyl, quinonyl;

d. a monoto hexavalent substituted heteroaromatic radical having up to carbon atoms selected from the group benzothiazolyl, phenyl,: thiophenyl, benzofuryl, N-methylcarbazolyl, quinolyl, quinonyl, pyridyl being substituted by at least one substituent selected from halogen, nitro, cyano, dialkylamino, diarylamino, alkylarylamino, alkyl, haloalkyl, alkylsulphonyl, alakoxy, alkylester, arylester, acyl, and cycloalkyl groups having up to 18 carbon atoms, a (w m) ketoalkyl radical having up to 5 carbon atoms;

wherein at least one nucleus of said aromatic nuclei may be quinoid and wherein polynuclear aromatic groups may be linked by aliphatic groups or by hetero atoms; and wherein the aromatic part of the radicals (b) to (d) is directly bound to the triketoimidazolidine nucleus and wherein in a compound of the formula (I) having only one triketoimidazolidine ring R is no phenyl or a halogen substitution product thereof if R' is phenylene or a halogenated phenylene group of hydrogen;

e. a group as defined for R wherein R may also be a mononuclear radical as defined under (a) and (b) in compounds having only one triketoimidazolidine nucleus;

f. a saturated aliphatic hydrocarbon radical having up to 18 carbon atoms;

g. a cycloaliphatic unsubstituted hydrocarbon radical having up to 12 carbon atoms;

h. a substituted cycloaliphatic hydrocarbon radical having 1 to 6 substituents and having up to 20 carbon atoms;

R" is a group as defined for R;

R is a group as defined for R' and at most tetravalent;

x=zero ify=1 or 1;

y zero or an integer from 1 to 70;

z an integer from 1 to 6; with the provisos that one of the groups R and R" is aromatic and if R is aliphatic or cycloaliphatic, the group R, R and R" adjacent to R' is aromatic, and that R and R have a meaning other than phenyl if m, n and y all equal zero.

R and R are preferably aliphatic hydrocarbon groups with up to 6 carbon atoms, e.g. alkyl groups, phenyl groups or phenyl groups substituted with alkyl groups having up to 6 carbon atoms.

In formula (I)- R, R, and R' may bevthe same or different; z is preferably 1 to 3and is at least 2 if m zero.

These compounds may be prepared without the above stated difficulties.

The compounds according to the invention corresponding toformula (I) can thus also be branched if R is branched. It is furthermore possible for the compounds to comprise only one triketoimidazolidine ring. This is the case if x or y are zero in the above formula. One then obtains compounds of formula wherein preferably R is a polynuclear cyclic, preferably aromatic group with up to 14 carbon atoms in the ring system, which group may be substituted, eg by acetyl, and wherein each nucleus can carry one to four or if m is zero up to five substituents, or a mononuclear cyclic group with up to 14 carbon atoms, with the proviso that R is not phenyl or the halogenation substitution products thereof if R' is a phenylene or halogenphenylene group or hydrogen;

R is a hydrocarbon ring with up to 20 carbon atoms, which may carry one to six and if n is zero up to five substituents in a ring and which is e.g. aromatic, straightchained or branched aliphatic or cycloaliphatic, and wherein Q and Q, m and n have the above-stated meaning.

Suitable R-groups in the compound according to formula II are, for example, phenyl, naphthyl, benzeneazophenyl, benzothiazolyphenyl, anthraquinonyl, pyridyl or cycloaliphatic groups, each of which can be substituted with one or more groups selected from alkyl, cycloalkyl or haloalkyl groups with up to 5 halogen atoms, alkoxy, acyl, aroyl, cycloalkyl or ester groups with up to 20 carbon atoms, alkyl or arylsulphonyl groups each with up to 15 carbon atoms, halogen atoms, trifluormethyl, acyl, such as acetyl groups, nitro and cyano groups.

Suitable groups R', in addition to the groups stated for R, are preferably phenyl or naphthyl or phenylene or naphthylene groups, each of which can be substituted with alkyl, haloalkyl with up to 5 halogen atoms, trifluormethyl, acyl such as acetyl, or nitro groups.

According to another feasible embodiment the compounds according to formula (I) can also be compounds of formula (III) (Ill) wherein R and R have the meaning stated for formula (I).

' Other compounds according to the invention are illustrated, by way of example, by the following formulae:

functionality, also R, R, R" and R in the compounds of formula (I) can be branched.

In the compounds according to formula (V) R, R,-

R', R, R", Q, Q, m, n, x,y, and 2 have the meanings defined above; a, v, and w can be independently zero or an integer from 1 to 70, at least one of u, v, and w being 1.

A further aspect of the invention provides a process for the preparation of a compound of general formula (I) wherein one of Q, Q is the group N- H-CO-OR and the other NH-CO-COOR, wherein R and R are aliphatic hydrocarbon groups with up to 18 carbon atoms, cycloaliphatic hydrocarbon groups with up to 8 carbon atoms, mononuclear aromatic hydrocarbon groups of 6 carbon atoms, or such mononuclear aromatic groups of 6 carbon atoms substituted with hydrocarbon groups having up to 14 carbon atoms, an urethane or an isocyanate group, and m and n each are independently zero or 1;

R is

a. monoor polynuclear monoto hexavalent unsubstituted aromatic radical having up to 14 carbon atoms;

b. a monoor polynuclear monoto hexavalent aromatic radical having up to carbon atoms being substituted by at least one substituent selected from halogen, nitro, cyano, dialkylamino, diarylamino, alkylarylamino, alkyl, haloalkyl,

alkylsulphonyl, alkoxy, alkylester, arylester, acyl,

and cycloalkyl groups having up to 18 carbon atoms, a (m m) ketoalkyl radical having up to 5 carbon atoms;

c. a monoto hexavalent unsubstituted heteroaromatic radical selected from the group benzothiazolyl, phenyl, thiophenyl, benzofuryl, N- methylcarbazolyl, quinolyl, pyridyl, quinonyl;

d. a monoto hexavalent substituted heteroaromatic radical having up to 20 carbon atoms selected from the group benzothiazolyl, phenyl, thiophenyl, benzofuryl, N-methylcarbazolyl, quinolyl, quinonyl, pyridyl being substituted by at least one substituent selected from halogen, nitro, cyano, dialkylamino, diarylamino, alkylarylamino, alkyl, haloalkyl, alkylsulphonyl, alkoxy, alkylester, arylester, acyl, and cycloalkyl groups having up to 18 carbon atoms, a (w m) ketoalkyl radical having up to 5 carbon atoms;

wherein at least one nucleus of said aromatic nuclei may be quinoid and wherein polynuclear aromatic groups may be linked by aliphatic groups or by hetero atoms; and wherein the aromatic part of the radicals (b) to (d) is directly bound to the triketoimidazolidine nucleus;

e. a group as defined for R;

f. a saturated aliphatic hydrocarbon radical hyving .up to 18 carbon atoms;

g. a cyloaliphatic unsubstituted hydrocarbon radical having up to 12 carbon atoms.

h. a substituted cycloaliphatic hydrocarbon radical having 1 to 6 substituents and having up to 20 carbon atoms;

7 8 R" is a group as defined for R; wherein r is an integer from 1 to 6, and R and R have R is a group as defined for R and at most tetravathe above meaning, are preferably reacted with isocyalent. nates of formula x=zero if =1 or I;

y zero or an integer from 1 to 70; 5 R (N C O)S z an integer from I to 6; wherein R' has the above meaning and s is an integer with the provisos that one of the groups R and R" is from 1 to 4, to form compounds of the general formula aromatic and if R"' is aliphatic or cycloaliphatic, the (I), wherein R, R, R', R", x and y have the above group R, R and R adjacent to R is aromatic which meaning but in which R and R' can also be phenyl if comprises reacting at least one ester of oxamidic acid 10 m, n and y are zero, whereupon, if desired, the polymwith the grouping -NHCOCO-OR, wherein R erisable groups formed are polymerised. As polymeriis as defined with an isocyanate or an isocyanate-formsation there is to be understood a chain elongation by ing compound at temperatures of -20 to +280C in means of addition and/or condensation.

the presence or absence of a catalyst. In this manner it is possible to prepare also without In the compound obtained according to this process polymerisation monomeric compounds with up to R is preferably a hydrocarbon group having and it may three triketoimidazolidine groups. This is the case also be substituted by isocyanate-forming compounds. when starting eg from monoisocyanates and tris- The triketoimidazolidines are thus obtained in high oxamidate esters. In the preparation of these comyields. pounds, however, care should be taken that amino The reaction can be performed, e.g., according to the radicals in the cyclic group R are not disposed in the following schemes (la) and (lb): o-position. Further products of this reaction are comif M wherein R R' and R have the meaning stated above. pounds according to the above formulae IV and V.

In this reaction, a completely novel cyclisation is When the starting material in the above reaction is a concerned in which one mol of the isocyanate serves as bisoxamidate ester of formula the condensation agent for splitting off the alcohol R CH. The oxamidate esters used as starting material may be obtained in known manner by reacting 6 Wm) monoor di-amines with oxalate esters, e.g., dialkyl 40 oxalates. The general formula (I) applies to products the novel bis-(2,4,5-tricetoimidazolidines) of formula VI obtained according to scheme (la), x and n being (III) are obtained in high yields according to the followzero in each case and z being 1. ing scheme:

Due to its excellent solubility, the carbamic acid (1c) 0 O O derivative formed as a by-product can readily be sepawherein R, R and R" have the above-defined meanrated. in conventional solvents, such as ligroin, benings and the two substituends R are preferably the zene, toluene ethanol, isopropanol, ether or tetrahysame but may be different. This can be the case if the drofuran, from the 2,4,S-tricetoimidazolidines which oxa idate est r ar reacted with eg a mixture of are mostly difficultly soluble in the above-stated Solisocyanates. Their synthesis according to the known vents. processes (1) (3) could only be performed with diffi- The process is equally suitable for the preparation of wh wi t the l w s lubility ot the bis-ureas resymmetrical, as well as of asymmetrical c bd, triketoimidazolidines.

oxamidate esters f f l In the reaction between the oxamidate esters and the 5 isocyanates with subsequent polymerisation, products having a relatively low degree of polymerisation are v R (NH CO CO OR (VII) obtained. In this reaction one mol of bis-oxamidate ester can react, for example, with one mol of diisocyanate analogously to scheme (1) only one isocyanate group being used, however, for the cyclisation, whilst the other assumes the role of the condensation agent, i.e. the alcohol liberated in the cyclisation, i.e. the alcohol liberated in the cyclisation is intramoleculary incorporated into compound II. This reaction takes place according to the scheme (Compound lX) In addition, however, also multiple forms of compound lX can be formed:

it H

A In these cases the alcohol liberated by the cyclisation can be taken up intramolecularly by the polymer and- /or extramolecularly by the still unsaturated isocyanate.

Common to all the compounds are the end groups R and R" can be difi'erent when a mixture of oxamidate esters with different alkyl groups is used. Further, the reaction of bis-oxamidate esters with diisocyanates can theoretically be expected to take place, e.g. as

follows:

ii iii The IR-spectroscopic examination of the reaction products obtained according to the invention clearly proved the presence of NHCOOR"'-groups. In addition, there was also found the band grouping characteristic for the 2,4,5-triketoimidazoline ring as a result of which the reaction according to formula scheme (2) is confirmed.

It is certain that in the process claimed, the polymers of scheme (3) are only formed in small quantities if the reaction conditions are chosen correctly. These polymers can indeed be recognised due to the fact that they are insoluble in the conventional solvents which contain no reactive protons (aprotic solvents) e.g. dimethylformamide, N-methylpyrrolidone, dimethylsulphoxide, N,N',N"-hexamethylphosphoric acid triamide). The products obtained according to the process claimed are, however, readily soluble in such solvents. Even 30-60% solutions can be obtained without difficulty in the above-mentioned aprotic solvents without the viscosity of said solutions being very high. The solutions also remain unchanged during storage and they do not tend to crystallise. These properties facilitate an extended use of the products prepared accord- .ing to the invention for obtaining heterocyclic polymeric products.

Specifically, if the monomeric compounds according to the invention, either in solution or free of solvent, are heated in the molten or solid state, at -550C preferably at 280-450C the end groups thereof react according to the following scheme (4) resulting in the formation of practically insoluble film-forming polymers which are resistant to chemical attack and remain unaffected by changes of temperature.

1 1 12 It is not necessary to use the reaction components in nature, i.e. a carbocyclic or heterocyclic group, prefera mixture; in fact it is also possible to carry out the ably with an aromatic character. It can be e.g. phenyl, reaction so that first one component is introduced, if naphthyl, benzeneazophenyl, benzothlazolylphenyl, desired, in admixture with only a minor portion of the anthraqulnonyl or pyridyl.

second component, and that the main quantity of the Suitable bifunctional groups R of the bis-oxamidate second component is then added. This method can be esters are e.g.

carried out either in solution or in the melt. The catawherein X is CH O-, -S SS lyst can in this case be added to the reaction compo- SO N=N, NR (R is here an allnent introduced first and/or to that used later. I 15 phatic, cycloaliphatic or aromatic group with up to 8 If the reaction temperature is chosen so high, e.g. carbon atoms), or R may be dlphenylene, dimethylfrom 150 to 300C, that the reaction of the end groups diphenylene, anthraquinonylene, pyridylene, quinonylene, quinolylene, thiophenylene, benzofurylene, and N-methylcarbazolylene groups. The group R- can fur- O 0 0 thermore carry one or more substituents in one or more H H ll aromatic and/or heterocyclic nuclei or in the side- NH CTC OR" and TNH TOR chain, so long as the substituents do not react with the isocyanates under the conditions of reaction employed.

proceeds at a sufficient speed, polymers insoluble in These substituents can be alkyl, alkbxy, haloalkyl, the aforesaid aprotonic solvents can be obtained in ter, alkylketo, ketoalkyl, or y p y many cases according to equ. (4). They can likewise be g p each With 5 -fl atoms, e e n In iS an separated off by filtration. They take the form of pale integer from 1 t0 Such 88 z s, a, yellow to brownish powders which are generally only 0C2H5, C 3, COOHC H CN, COCH soluble in hot concentrated sulphuric acid. They are z a; the substitueqts m y be ni O cyano separated, practically unchanged, from this solution by 0 g p or halogen, especially F, B1 In 8 811111131 addition of, e.g., water. manner also tris and/or tetrakis-oxamidate esters can The compounds claimed are obtained as powders or be used by themselves alone or in mixture w1th the as crystalline, e.g. also microcrystalline, substances. biS-OXamidate P a In compounds IV and V the same groups as in com- The group R"' 1n the isocyanates 1s monoto tetravapound II can form the end groups. It is, however, also leflt, -gabbhatlb, cycloablbhatlc, aromatlc or possible to have oxamidate ester groups on both sides mlXeCl aromatic-aliphatic group with up to P or these ester groups on only one side, and either urebly up to 15 C-atoms, e.g. cyclohexyl, butyl, octyl, thane or isocyanate groups on the other side, or ureoctadecyl, or

thane or isocyanate groups on both sides. or ethylene, propylene, butylene, or

rim CH3 -cn c CH2 CH-CH2-CH2 H3C cu c ii The reaction according to scheme (4) is a condensa- These groups may carry one or more substituents, e.g. tion, whilst reaction (3) is an addition followed by a at least one selected from alkyl, alkoxy or haloalkyl condensation. groups each with up to 5 C-atoms, or nitro groups,

As it is clearly apparent, the new process permits the halogen, especially F, Cl, Br, e.g. CH C H reaction of entirely different starting materials. The s z s 0r R1 and wherein Several products thereof may be used for an extremely large matic rings can be linked y 2-, s number of purposes. SS, SO CO- or -N=N-.

The high chemical uniformity of the polymers ob- If monomeric products are desired, at least one tained is shown by the outstanding ability to form films monofunctional reaction component will be used as and foils. The thermal stability is particularly high in starting material, e.g. monoisocyanates or monooxamiproducts having a low hydrogen content, especially date esters. however, in the absence of aliphatically or cycloali- Preferably not more than 5 H-atoms are substituted phatically bonded hydrogen in the heterocycle system. by such groups in each radical R.

. The films and foils which are obtained from the above R and R in the oxamidate esters used are alkyl intermediates are further distinguished by very good groups with up to 6 carbon atoms, preferably CH elasticity properties. C H C H phenyl groups which can be substi- The R-group in the oxamidate esters is of an aromatic tuted with the aforenamed alkyl groups. Suitable trior 13 tetrahydric isocyanates are e.g. 2,4,6-triisocyanotoluene, 4.4',4"-triisocyanotriphenylmethane, 2,4,4"- triisocyanodiphenylmethane, ,5,5 '-tetraisocyanodiphenylmethane, or trihydric isocyanates of formula C 2 o CO NHQ 'Q; NCO

which may be obtained, for example, by addition of trimethylolpropane to tolylene diisocyanate, an isocyanate which may be prepared by reaction of hexamethylenediisocyanate and water, of formula 14 chlorobenzene, nitrobenzene, cyclohexane, ethyl acetate, butyl acetate or 2) also in those solvents in which the reaction products are soluble, such as N,N'-dimethylforrnamide, N,N-dimethylacetamide, dimethylsulphoxide, N-methylpyrrolidone, N,N,N"-hexamethyl phosphoric acid triamide, phosphoric acidtris-(dimethylamide), cyclohexanone, isophorone, acetophenone, or in phenols with up to 10 carbon atoms, e.g. phenol, cresol or xylenol.

In addition to the solvents already mentioned, the products are also soluble in ketones, such as'acetone, methylethylketone, or dibutylketone.

A further advantage of the present process resides in v the possibility of synthesising one and the same asym- O H: NH(CH2)6-NCO (Xll) OCN(CH N C- NH- CH NC0 or isocyanates with up to four free rsocyanate groups of formula NC 0 H3C c H i if H (c 2 )6\ c T T T/ \T NC (I C\ C \N/ N/ Nco i Nco c H CH 3 such as may be prepared e.g. by reacting tolylene diisocyanate and hexamethylene diisocyanate.

Also thetriand tetraisocyanates can comprise the same above-stated substituents as the diisocyanates.

In place of the free isocyanates, also compounds forming isocyanates can be used, e.g. diphenylmethane-4,4'-bis(carbamic acid phenyl ester), diphenylethane-4,4'-bis(carbamic acid butyl ester) or diphenyl- 4,4'-bis(carbarnic acid diethylamide).

The polyisocyanates are generally reacted with the bis-oxamidates in the mol ratio of 1:0.5 to 4, preferably 1:0.8 to 2.2, in particular 1:09 to 1.5. The reaction can take place in the melt, particulary in the presence of solvents, preferably first in the melt and then in phenolic solvents. The reaction can take place e.g. l) in such solvents in which the reaction products of the invention are insoluble, e.g. in ligroin, benzene, toluene, xylene,

metrically substituted 2,4,S-triketoimidazolidine from different starting materials. Thus e.g. the following compound (Xlll) I or a can on the one hand be prepared from p-chlorophenylisocyanate and ethyl N-( 1-naphthyl)-oxamidate or on the other hand from l-naphthylisocyanate and methyl N-(p-chlorophenyl)oxamidate. It thus becomes possible to select the most favourable reaction components in each case.

The reaction according to the invention can take place in the absence or advantageously in the presence of solvents at temperatures from minus 20 to plus 280C, preferably at to 180C. The reaction is exothermic and proceeds in many cases even at room temperature or at a slightly elevated temperature, e.g. even at 40 to 50C. For completing the reaction and when using less reactive components, e.g. some isocyanates, heating can at times be recommended. It is also possible to react the starting materials in the melt and thereafter, if desired, in phenolic solvents. Products of a particularly high quality are thus obtained.

dibutyl tin glycolate, dibutyl tin dilaurate, diphenyl tin oxide, ferrocene (dicyclopentadienyliron (11), metal chelates, such as iron acetylacetonate or cobalt complexes, or mixtures of any of the aforementioned compounds.

The yields of N,N-disubstituted 2,4,5-

triketoimidazolines in the present process vary generally between 65 and 98 of theory.

The monomeric and polymeric, especially the low-;

molecular weight compounds prepared according to the invention are valuable intermediates for organic syntheses. They may be used as starting materials for the preparation of pharmaceuticals, pest control agents, such as insecticides, fungicides, mycocides and bactericides, for the synthesis of dyestufi's and synthetic resins and for stabilising high molecular weight substances, particularly polymerisation and condensation resins.

The products and polymers prepared according to the invention are also suitable in particular for the coating of metallic shaped articles, such as wires, metal sheets, plates and pipes, it being immaterial whether the application takes place in the powder form or in solution. They can, however, also be applied in the same way to ceramic shaped articles. After the thermal polycondensation, well-adherent and thermally stable coatings are obtained on these articles. The compounds of the invention are also suitable, however, especially in the powder form, and after mixing them with fillers,

e.g. glass flour, glass fibres, asbestos fibres, metal powders or metal chips, for the production of moulded articles according to the hotpress process. Furthermore glass-clear foils and films as well as fibres can be produced therefrom. By suitable means e. g. the addition of expanding agents, the products can be converted to a foam-like material which is stable at high temperatures. The products obtained according to the invention are also suitable as stabilisers for polymeric products, especially for polymerisation and/or polycondensation resins. They can, however, also be mixed with such polymers including polymerisation and/or polycondensation resins having heterocyclic groups, at temperatures between minus to plus 250C, preferably at to 190, in a solution, in the melt or in the solid phase,

and worked up further to moulded articles or coatings. In order that the invention may be better understood, the following examples are given by way of illustration l,4-Bis-[N-( N'-( 3-chlorophenyl)-2,4,5- triketoimidazolidyl)]-benzene EXAMPLE] 0 0 II n l V O 30.8 g of N,N'-bis-ethoxalyl-p-phenylenediamine (0.1 mol), m.p. 212C, and 61.4 g of m-chlorophenylisocyanate (0.4 mol) are heated at C with 350 ml of xylene and 60 ml of N,N-dimethylacetamide. A solution of 1 g of tri-n-butylamine in 20 ml of alcohol is then queckly stirred in. The temperature then rises by a few degrees. The reaction mixture is then boiled under reflux for 5 hours. The separation of a heavy, light-yellow powder starts after a few minutes. The product is filtered off after cooling, washed with hot xylene and hot n-butanol and dried at C.

Yield: 51.5 g (98% of theory). No melting under 360C.

The substance can be recrystallised from cyclohexanone/N-methylpyrrolidone to form colourless microscopically small needles.

found calculated Analysis:

The lR-spectrum clearly shows the band grouping de- EXAMPLE 2 o o 11 H o 0 Cl 11 II 11 ll 0 o 17 1 ,3-Bis-[N-(N-(3-chloropheny1)-2,4,5- triketoimidazolidyl)]-benzene The compound is prepared from N,N-bis-ethoxa1ylm-phenylenediamine and m-chlorophenylisocyanate by the method described in Example 31. In place of N,N-dimethy1acetamide, however, 30 ml of N-methyl pyrrolidone are used.

Yield: 94% of theory. M.p. 304-306C (darken- 18 (0.1 mol; m.p. 179C), and 47.6 g of phenylisocyanate (0.4 mol) are boiled under reflux for 3 hours with 250 ml of xylene, 50 ml of chlorobenzene and 2.5 ml of tri-n-butylamine. The precipitated product is filtered ofiwith suction, washed with xylene and dried at Yield: 50.0 g (90% of theory). M.p. 300C.

M'.P. after recrystallisation from cyclohexanoneldimethylformamide 304C.

4,4-Bis-[N-(N-(3-chlorophenyl)-2,4,5- triketoimidazolidyl ]-diphenyl 38.4 g of N,N-bis-ethoxaly1-benzidine (0.1 mol),

mp. 218C, are refluxed for 3 hours with 61.4 g of m-chlorophenylisocyanate (0.4 mol), 600 ml of xylene, 60 ml of N,N',N"-hexamethylphosphoric acid tn'amide and 2 ml of triethylamine. After cooling, the sandy, 40

yellowish powder is filtered with suction.

Yield: 54.6 g (90% of theory). No melting below 360C.

The comparison of the IR-spectra of this hexacyclic compound with the pentacyclic compound prepared according to Example 31 shows identity in the bands mentioned in Example 2.

EXAMPLE 4 H 3 CH3 acfi N N-- N N II, I

41.2 g of N ,N -ethoxa1yl-3 ,3 -dimethy1-benzidine Analysis: found calculated EXAMPLE 5 1,5-Bis-[N-( N'-( 3-chloropheny1)-2,4,5- triketoimidazolidyl)]-naphtha1ene 35.8 g of N,N'-bis-ethoxalyl-naphthylene-1,S-diamine (0.1 mol, m.p. 213C) are boiled under reflux for 6 hours with 61.4 g of m-chlorophenylisocyanate (0.4 mol), 500 ml of benzene, m1 of dimethyl formamide and 3 m1 of triethylamine. The heavy grey powder which separates is filtered off with suction, washed with toluene and isopropanol and dried at C.

Yield: 39.9 g (68% of theory). No melting below EXAMPLE 6 ob o o o 19 4,4-Bis-[N-(Nphenyl)2,4,5-triketoimidazolidyl]- diphenyl ether 20.0 g of N,N'-bis-ethoxalyl-4,4-diaminodiphenylether (0.05 mol; mp. 154C), 100 ml oftoluene, 3 ml of N,N-dimethylacetamide 23.8 g of phenylisocyanate (0.2 mol) and 1 ml of triisopropylamine are heated under reflux for 4 hours. 200 ml of ligroin and 100 ml of toluene arethen added and the reaction mixture is filtered hot after addition of 3 g of activated charcoal. The product crystallises out after cooling to about 5C.

Yield: 25.0 g (91 of theory). M.p.=267272C.

M.p. after recrystallisation from Xylene/ligroin (2:1), m.p.=278C.

The IR-spectrum shows band groupings in very good conformity with those described in Example 2. The NH-bands are absent.

EXAMPLE 7 398 g (1 mol) of bis-N,N'-ethoxalyl-4,4'-diaminodiphenylmethane are first stirred for 1 hour at room temperature under a protective gas (N or CO with 252 g (1 mol) of 4,4-di-isocyano-diphenyl ether in 250 g of N,N-dimethylformamide and 400 g of N-methylpyrrolidone. A solution of ml of triethylamine and 0.3 g of cobalt naphthenate in 50 ml of N,N'-dimethylformamide is then added dropwise so that the temperature does not exceed 50C.After the exothermal reaction has subsided stirring is continued for 3 further hours. A pale yellow solution is obtained which has a viscosity of 1200-1300 cP (20C). If metal sheets are coated in known manner with this solution, and the layer is stoved for 5 minutes at 375C, clear, elastic and well adherent coatings having an outstanding resistance to solvents and chemical attack are obtained.

EXAMPLE 8 308 g (1 mol) of l,4-di-ethoxalylamino-benzene are dissolved at room temperature, with 250 g (1 mol) of 4,4'-diisocyano-diphenylmethane in 400 g of N,N- dimethylacetamide, and 158 g of N,N, N-"-hexamethylphosphoric acid triamide and 5 ml of triethylamide are added. The temperature then rises to about 70C. The initially mobile liquid turns gradually more viscous. After the exothermal reaction has subsided, stirring is continued for 2 further hours at 80C. The tenninal viscosity of the solution is 2000 to 2500 cP (20C).

Copper wires coated with this solution yield, after a thermal treatment for 160 seconds at 430C, clear, well-adherent coatings with a high chemical thermal stability.

EXAMPLE 9 384 g (1 mol) of 4,4'-di-ethoxalylamino-diphenyl and 202 g 1.2 mol) of 1,6-di-isocyanohexane are kept for 1 hour at 150C with 5 g of N-methylmorpholine and 0.5 g of iron acetylacetonate. 293 g of dimethylsulphoxide are then stirred in and stirring is continued for 4 further hours at 100C.

The pale brown solution obtained yields, on application to metal surfaces and thermal treatment at 240C, clear, pale brown and elastic coatings.

EXAMPLE 10 400 g (1 mol) of 4,4'-di-ethoxalylamino-diphenyl ether and 174 g (1 mol) of tolylene 2,4-diisocyanate are stirred together at 50C. 3 ml of tri-n-butylamine are then added. By cooling, the temperature is kept below 80C. 574 g of N-methylpyrrolidone are then 20 added quickly. After stirring for 5 hours at -80C, a clear, pale yellow solution of medium viscosity is obtained-(15004800 cP, 20C). Upon stoving a coating of this solution on unglazed hard white ware at 420C, clear, orange-brown, well-adherentcoatings of a high thermal stability are obtained.

EXAMPLE 1 l becomes almost clear in the course of 4 hours. It is filtered through a pressure filter, whereupon a clear, orange-yellow solution is obtained. Clear, hard films are obtained upon stoving this solution on glass plates at 375C.

EXAMPLE 12 444 g (1 mol) of 4,4-di-ethoxalylamino-3,3-dimethoxydiphenyl are dissolved with stirring in g of N,N-dimethylaniline and 700 g of N,N-dimethylformamide. A solution of 252 g ,(1 mol) of 4,4- diisocyanodiphenyl ether in 1500 ml of xylene is then added at 50C and the temperature raised to C. The initially clear solution turns more cloudy and the separation of a light-yellow substance starts. After several hours the mixture is cooled to room temperature, and the solid product is filtered off, washed with toluene and dried in vacuo at 70C.

Yield: 622 g (89 of theory). The pale yellow powder obtained is readily soluble in N,N-dimethylacetamide, dimethylsulphoxide and N-methylpyrrolidone. Upon stoving at 320350C, the solutions yield clear, elastic coatings on metallic surfaces which can only be dissolved in warm, concentrated sulphuric acid.

EXAMPLE 13 diisocyano-diphenylmethane are then stirred in. After.

homogenising well, 5 ml of triisopropylamine and 0.2 g of tris(carboxyethyl)phosphine are added. The temperature rises to about 70C. The reaction mixture is then stirred until the exothermal reaction subsides and the temperature drops to 50C. Stirring is continued at this temperature for 3 further hours. The pale yellow viscous solution is suitable in this form for the coating of metallic surfaces. Stoving can take place at 325430C. The clear, brownish-yellow coats are very stable even at high temperatures. The loss of weight amounts to less than 3% at 400C after 5 minutes in the atmosphere. The thermal continuous load at 325C in the atmosphere exceeds 15 hours.

EXAMPLE 14 322 g 1 mol) of 1,3-di-ethoxalylamino-2-methylbenzene and 279 g (1.6 mol) of tolylene-2,4-diisocyanate are stirred at room temperature with 400 g of N- methylpyrrolidone, and 50 g of isophorone and 10 g of triethylamine are added. After adding the catalyst, the temperature rises to 5060C. The initially cloudy reaction mixture turns clear. If no heat is supplied, the reaction is completed after stirring for 4-6 hours. The

solution obtained may be used for the manufacture of coatings which are highly resistant to changes of temperature.

EXAMPLE found calculated C 64.67 64.28 H 3.38 2.88 O 22.10 22.84 N 10.00 10.00

which are consistent with the structure:

Neither urethane nor ester nor -NH groups could be traced in the IR-spectrum.

EXAMPLE 16 mgs.

EXAMPLE 17 448 g (1 mol) of 4,4-di-ethoxalylamino-diphenylsulphone are stirred with 250 g of N,N,N-hexamethylphosphoric acid triamide and 450 g of N-methylpyrrolidone with addition of 10 g of triethylenediamine,

whereby a paste is formed. 252 g (1 mol) of 4,4-diisocyanodiphenyl ether are then so added that the temperature does not exceed 60C. The initially thin paste thus turns into a clear solution with a moderate viscosity. The reaction is completed by stirring for 8 hours more. Upon heating on metallic surfaces (10 mins., 325C), the solution yields clear films which are extremely stable to organic solvents.

22 EXAMPLE 1% 796 g (2 mol) of the bis-oxamidate ester of 4,4- diarninodiphenylmethane are melted with stirring for 6 hours at C with 500 g (2 mol) of 4,4-diisocyanodiphenylmethane. 1296 g of a cresol mixture and 2 ml of dibutyl tin laurate are then added and the reaction mixture is then heated for a further 3 hours at 200210C. After cooling, a clear, red-brown, highly viscous solution of the polymer is obtained.

Yield: 2500 g.

EXAMPLE 19 800 g (2 mol) of bis-oxamidate of 4,4'-diaminodiphenyl ether are heated for 6 hours at 200220C with a mixture of 375 g of 4,4-diisocyano-diphenylmethane, 126 g of 4,4-diisocyano-dipheny1 ether and 0.3 g. of diazabicyclooctane. The melt is then poured at C on to metal sheets. The material obtained after cooling is pulverised.

Yield: 1280 g. (softening range 120135C).

The yellow powder is readily soluble in aprotnoic solvents, cyclohexanone and phenolic mixtures.

EXAMPLE 20 A mixture of 398 g. (1 mol) of the bis-oxamidate ester of 4,4'-diamino-diphenylmethane and 400 g. 1 mol) of the bis-oxamidate of 4,4'diaminodiphenyl ether is melted at 140C for 2 hours with 500 g. of 4,4'-diisocyano-diphenyl ether. After adding 0.1 g. of lithium phenolate the temperature is raised during 2 hours to 200C and the mixture stirred for 6 hours more at 200210C. After cooling to C, 1500 g. of N-methylpyrrolidone are stirred in. A clear, yellow-red viscous solution is obtained.

Yield: 2730 g.

EXAMPLE 21 O O H c H u cl 0 265 g. (1 mol) of ethyl(p-diethylaminophenyl)- oxamidate (melting point 73C, light-yellow colored) are dissolved in 500 ml. of toluene and mixed at room temperature with 5 ml. of triethylamine.

310 g. (2 mol) of m-chlorophenylisocyanate are then added. The reaction is exothermic. To complete the reaction the reaction mixture is boiled under reflux for 6 hours. 350 ml. of toluene are then distilled off, the residue is diluted with 250 ml. of toluene, filtered with suction and washed with a ligroin-toluene (70:30) mixture. After drying in vacuo 260 g. of the above heavy orange-red colored compound are obtained.

Yield: 70% of theory, melting poinFl27-128C.

A sample recrystallised twice from cyclohexane-toluene yielded the following analysis found calculated 23 24 EXAMPLE 22 sulphoxide are then stirred in and stirring is continued II II /cc\ s N\c/N CH2 H3C (I) ii I? m -N N c ll 5 CH 0 68 g of ethyl N- [4-(6-methyl-benzothiazolyl)-phenyl] for 4 further hours at 100C.

oxamidate (0.2 mol) and 50 g of diphenylmethane A pale brown solution is obtained which may be diisocyanate (0.2 mol), 500 ml tolyene and 1 m of applied to metal surfaces. After thermal treatment at triethylamine are boiled under reflux for 25 minutes. 240C a clear pale brown and elastic coating is ob- The paste of crystals formed is filtered with suction and tained. It has compared with the coating of example washed with toluene. 39 an essentially improved surface hardness and Yield: 147.5 g (88% of theory). resistence to solvents.

What we claim is: EXAMPLE 23 1. A compound of formula 0 o 25 CI II II o o c l n ll 1; ll 1' R-N N-R -N NR' u ll CM 0 c o l H co 0 o 269 g of ethyl (8-methoXy-4-chloro-chinolyl)-3- wherein R and R are phenyl or naphthyl that are oxamidate 1 mol) and 144 g of m-cyanophenylisocyaunsubstituted or monosubstituted with nitro, halo, nate 1 mol) are boiled under reflux for 5 hours at 150 lower alkyl, lower alkoxy or haloalkyl; R and R' being to 155C with 300ml of chlorobenzene. After cooling the same or different and R is the product crystallises out in pale yellow crystals that is unsubstituted or mono-substituted with lower which are filtered and washed with toluene. alkyl, lower alkoxy, halo, nitro or haloalkyl, and

Yield: 310 g 84 of theory). The product is wherein x is a bond, CH 0, S or sulphonylene. recrystallised from cyclohexanone/n-butanol. 2. A compound of claim 1 wherein R and R are phenyl or naphthyl radicals at least one of which being EXAMPLE 24 substituted by halogen, R is a bivalent polynuclear 384 g (1 mol) of 4,4-di-ethoxalylaminodiphenyl, carbocyclic aromatic radical having up to 14 carbon 197 g 1.17 mol) of 1,6-di-isocyanohexane and 25 g atoms,

( Of the isocyanate of formula XIII are p 3. A compound of formula of claim 1 wherein R and for 1 hour at 150C with 5 g of N-methylmorpholine R are m-chlorophenyl and R is diphenylene. and 0.5 g of iron acetylacetonate. 293 g of dimethyl- 4. A compound of the formula N N ll 0 26 S. A compound of the formula 0 0 Cl 2 I If c l 1 M c \c is a 6. A compound of formula J M i K,

wherein R' is phenyl or napththyl that is unsubstituted that is unsubstituted or mono-substituted with lower or monosubstituted with nitro, halo, lower alkyl, lower alkyl, lower alkoxy, halo, nitro', or CB, and wherein X alkoxy or CF, and R is is a bond, CH 0, or S.

Page 1 of 4 UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION December 23, 1975 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Col. 2, line 39,

C01. 2, line 40,

C01. 2, line 45,

C01. 3, line Col. 3, line 28,

C01. 3, line 35,

C01. 3, line 52, or 1 if y Col. 3, line 56,

l Col. 5, line 38,

C01. 5, line 57,

Col. 6, line 56,

C01. 7, line 4, or 1 if y I Col. 7, line 7,

Col. 7, line 16,

delete "an" and insert a delete "each".

delete "readical" and insert radical I delete "alakoxy" and insert alkoxy delete "quinoid" and insert quinonoid delete "of" and insert or C I delete if y l or 1;" and insert delete "if y .l or 1;" and insert A delete "provisos" and insert proviso delete "having'h" Page 2 of 2 UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION DATED December 23, 1975 INVENTOMS) Johannes Reese It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Col. 7, line 56, delete after rated. 7 Col. 7, line 58, delete "tricetoimidazolidines" and insert triketoimidazolidines G Col. 8, line 41, delete "tricetoimidazolidines" and insert triketoimidazolidines Col. 8, line 56, delete "substituends" and insert substituents Col. 8, line 61, delete "0t" and insert of I Col. 9, line 5, delete "i.e. the alcohol liberated in the cyclisation,". Y

0 Col. 10, in formula (4) the horizonal line before (nR -OH nR OH) is a minus sign, not a bond.

Col. 12, the formula between lines 44 and 53,

a I II -Cl i (I CH CH CH CH I 3 4 a 4 has a bond between CH and CH.

Page 3 of 3 UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION Q PATENT NO. 1 3 92 37 DATED December 23, 1975 INVENTOMS) I Johannes Reese It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Col. 12, line 57, delete "CF and insert; CF

Col. 13, line 2, insert after the first 4.

5 Col. 13, line 3, insert 2,2 before ,5,5'

Col. 13, line 64, delete "particulary" and insert particularly Col. 15, line 33, delete "di cyclopentadienyliron" 0 and insert dicyclopentadienyl-iron Col. 16, line 40, delete "queckly" and insert quickly Col. 16, lines 56 -59, delete "The I-R-spectrum clearly shows the band grouping described in Example 2. C Ester bands and NH-bands are completely absent."

Col. 17, line 6, delete ".31" and insert --v l Col. 17, lines 44-47, delete "The comparison of the IR-spectra of this hexacyclic compound with the pentacyclic compound compared to Example 31 shows identity in the bands mentioned in Example 2.

Col. 19, lines 14-16, delete "The IR-spectrum shows band groupings in very good conformity with those I described in Example 2. The NH-bands are absent.

. Page 4 pf'4 UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,928,376 v I I I DATED 3 'December 23, 1975 Johannes Reese lNV ENTOR(S) It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Col. 21, line 51, delete after then.

7 Col. 22, line 22, delete "aprotnoic" and insert aprotic v g Col. 23, line 18, delete "tolyene" and insert toluene Col. 24, line 21, delete "39" and insert 9 Col. 24, line 36, after "haloalkyl" add or m methylb'enzthiazolyl Col. 24, last line of the formula at the bottom of the column intensify the bottom 9 of the structure.

. v M Signed and Scaled this T yh -.D y Of August 1976 [SEAL] I I Arrest:

numc.-msou OMARSHALLDANN Anesn'ng Offieer I (ommissirmerofParenIs and Trademarks 

1. A COMPOUND OF FORMULA
 2. A compound of claim 1 wherein R and R'''''' are phenyl or naphthyl radicals at least one of which being substituted by halogen, R'' is a bivalent polynuclear carbocyclic aromatic radical having up to 14 carbon atoms.
 3. A compound of formula of claim 1 wherein R and R'''''' are m-chlorophenyl and R'' is diphenylene.
 4. A compound of the formula
 5. A compound of the formula
 6. A compound of formula 